EP1355952A1 - Method for producing a catalyst for homo- or co- polymerization of ethylene - Google Patents
Method for producing a catalyst for homo- or co- polymerization of ethyleneInfo
- Publication number
- EP1355952A1 EP1355952A1 EP01983847A EP01983847A EP1355952A1 EP 1355952 A1 EP1355952 A1 EP 1355952A1 EP 01983847 A EP01983847 A EP 01983847A EP 01983847 A EP01983847 A EP 01983847A EP 1355952 A1 EP1355952 A1 EP 1355952A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxy
- group
- polymerization
- ethyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/612—Pretreating with metals or metal-containing compounds
- C08F4/616—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Definitions
- the present invention provides a method for producing a catalyst for homo-polymerization or co-polymerization of ethylene, or more particularly a method for producing a high-activity titanium solid complex catalyst supported on a carrier containing magnesium, wherein said catalyst is capable of producing polymers of high bulk density and narrow particle size distribution with low content of fine particles.
- Catalysts containing magnesium for polymerization or co-polymerization of ethylene are known to have very high catalytic activities and to accord polymers of high bulk density, which are suitable for liquid phase or gas phase polymerization.
- liquid phase polymerization of ethylene it denotes a polymerization process performed in a medium such as bulk ethylene, isopentane, or hexane, and as for the important characteristics of catalysts used in this process, there are as follows: high catalytic activity, bulk density of the resultant polymers, the content of low molecular weight molecules of the resultant polymers dissolved in a medium, the particle distribution of the resultant polymers, and the existence of fine particles within the resultant polymers.
- catalysts containing magnesium by reacting the said liquid-phase magnesium solution with a halogenated compound such as titanium tetrachloride are well known.
- a halogenated compound such as titanium tetrachloride
- Such catalysts provide high bulk density to the resultant polymers, but there is much yet to be improved with respect to their catalytic activities or hydrogen reactivities.
- tetrahydrofuran, a cyclic ester has been used as a solvent for a magnesium compound in US Patent Nos. 4,477,639 and 4,518,706.
- US Patent No. 5,459,116 has reported a method of production of a titanium solid catalyst by contact-reacting a magnesium solution containing an ester having at least one hydroxyl group as an electron donor with a titanium compound. By this method, it is possible to obtain a catalyst of high polymerization activity, which accords high bulk density to resultant polymers, but there is room for yet more improvements.
- the objective of the present invention is to provide a new method for producing a catalyst for homo-polymerization or co-polymerization of ethylene, wherein said catalyst has high catalytic activity, which is capable of producing polymers of high bulk density and narrow particle size distribution with few fine particles.
- Another objective of the present invention is to provide a simple process for producing a catalyst for homo-polymerization or co-polymerization of ethylene.
- the catalyst for homo-polymerization or co-polymerization of ethylene according to the present invention is produced by a simple yet efficient manufacturing process, which comprises (i) preparing a magnesium solution by contact-reacting a halogenated magnesium compound with alcohol, and adding mineral oil to adjust the viscosity of said magnesium solution; (ii) reacting said solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group; and ( ⁇ i) producing a solid titanium catalyst by adding a mixture of a titanium compound and a silicon compound.
- Types of halogenated magnesium compounds used in the present invention are as follows: di-halogenated magnesiums such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; alkymagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, and amylmagnesium halide; alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagensium halide, isopropoxymagnesium halide, butoxymagnesium halide, octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methyl-phenoxymagnesium halide.
- di-halogenated magnesiums such as magnesium chloride, magnesium io
- the following compounds can be used in the present invention: such compounds obtained by reacting magnesium compounds with polysilolxane compounds, silane compounds containing halogen, ester, or alcohol; and such compounds obtained by reacting magnesium metals with alcohol, phenol, or ether in the presence of halosilane, phosphorus pentachloride, or thionyl chloride.
- the preferable magnesium compounds are magnesium halides, especially magnesium chloride or alkylmagnesium chloride, preferably those having respectively an alkyl group of 1 ⁇ 10 carbons; alkoxymagnesium chlorides, preferably those having respectively 1 - 10 carbons; and aryloxymagnesium chlorides, preferably those having respectively 6 - 20 carbons.
- the magnesium solution used in the present invention can be produced as solution by using the aforementioned magnesium compounds in the presence a hydrocarbon solvent or in the absence thereof, in an alcohol solvent.
- hydrocarbon solvents used in the present invention include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.
- aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene
- alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene,
- alcohol When a magnesium compound is converted into a magnesium solution, alcohol is used in the presence of the aforementioned hydrocarbons or in the absence thereof.
- the types of alcohol include those containing 1 - 20 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl benzyl alcohol, and cumyl-alcohol, although alcohol containing 1 - 12 carbon atoms is preferable.
- the average size of a target catalyst and its particle distribution can vary according to the types of alcohol, the total contents, the types of magnesium compounds, and the ratio of magnesium to alcohol, etc. Nevertheless, the total amount of alcohol required to obtain the magnesium solution is at least 0.5 mol per each mole of magnesium compounds, preferably about 1.0 - 20 mol, or more preferably about 2.0 - 10 mol.
- the reaction of a magnesium compound with alcohol is preferably carried out in the presence of a hydrocarbon medium.
- the reaction temperature while variable depending on the types and the amount of alcohol, is at least about - 25°C, preferably -10 - 200°C, or more preferably about 0 - 150°C. It is preferable to carry out the reaction for about 15 minutes - 5 hours, preferably for about 30 minutes - 4 hours.
- mineral oil white oil, p-irafinic hydrocarbon oil (e.g., Nujol), or silicone oil can be used.
- the viscosity of mineral oil used in the present invention is 5-85 centistoke at 40°C, or preferably 60-75 centistoke.
- the ester compounds respectively having at least one hydroxyl group include unsaturated aliphatic acid esters respectively having at least one hydroxyl group, such as 2-hydroxy ethylaciylate, 2-hydroxy ethylmethacrylate, 2- hydroxypropyl acrylate, 2-hydroxypropylmethacrylate, 4-hydroxy butylacrylate, pentae--ythritol tiiacrylate; aliphatic monoesters or polyesters respectively having at least one hydroxyl group, such as 2-hydroxy ethyl acetate, methyl 3-hydroxy butylate, ethyl 3-hydroxy butylate, methyl 2- hydroxy isobutylate, ethyl 2-hydroxy isobutylate, methyl-3-hydroxy-2-methyl propionate, 2,2- dimethyl-3-hydroxy propionate, ethyl-6-hydroxy hexanoate, t-butyl-2-hydroxy isobutylate, diethyl-3-hydroxy glutarate
- a compound which is represented by a general formula of R n S ⁇ OR) ⁇ (here R is a hydrocarbon having 1-12 carbons, while “ri” is a natural number from 0 to 3) is preferable.
- the following compounds can be used: dimethyldj-methoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethylt-rimethoxysilane, vinyl-rimethoxysilane, memyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate, butylsilicate, methyltriaryloxysilane, etc.
- the amount of said compound is preferably 0.05 ⁇ 3mol per mole of magnesium, or more preferably 0.1 ⁇ 2mol.
- the temperature for the contact-reaction of the magnesium solution an ester compound having at least one hydroxyl group, and an alkoxy silicon compound
- the temperature of 0 - 100 ° C is appropriate, or more preferably 10 - 70 ° C.
- the magnesium compound solution obtained as such is reacted with a mixture of a liquid titanium compound represented by a general formula of Ti(OR) a 4 - a (here R is a hydrocarbon group, X a halogen atom, "a" a natural number from 0 to 4) and a compound represented by a general formula of R n SiC - n (here R is hydrogen, an alkyl group, an alkoxy, haloalkyl, or aryl group having 1—10 carbons, or halosilyl or a halosilylalkyl group having 1 ⁇ 8 carbons, and "n" a natural number from 0 to 3).
- R is an alkyl group having 1—10 carbon atoms.
- the types of titanium compounds which satisfy the general formula include 4-halogenated titanium such as TiC- , TiBr , and Til t ; 3-halogenated alkoxy-titanium such as Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and Ti(O(i-C 4 H 9 ))Br 3 ; 2-halogenated alkoxy-titanium compounds such as Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(O(i-G ⁇ H 9 )) 2 Cl 2 , and Ti(OC 2 H 5 ) 2 Br 2 ; and tetra-alkoxy titanium such as Ti(OCH 3 ) 4 , Ti(OC 2 H 5 ) 4 , and Ti(OG ⁇ H 9 ) 4 .
- a mixture of the above titanium compounds can also be used in the present invention.
- the preferable titanium compounds are those containing respectively
- n (here R is hydrogen, an alkyl group, an alkoxy, haloalkyl, or aryl group having 1-10 carbons, or halosilyl or a halosilylalkyl group having 1-8 carbons, and "n" a natural number from 0 to 3) include silicon tetrachloride; trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane; dichlorosilanes such as dimethyldichlorosilane, diethyldichlorosilane, di- phenyldichlorosilane, and methylphenyldichlorosilane; monochlorosilanes such as trimethylchlorosilane; and a mixture of these silicon compounds can also be used in the present invention, or more preferably silicon tet
- the amount of mixture of a titanium compound and a silicon compound used during re- crystallization of magnesium compound solution is appropriately 0.1 - 200 mol per mole of magnesium compounds, preferably 0.1 - 100 mol, or more preferably 0.2 - 80 mol.
- the molar ratio of the titanium compound to the silicon compound in mixture is appropriately 1 :0.05
- the reaction of the magnesium compound solution with the mixture of a titanium compound and a silicon compound should be carried out preferably at a sufficiently low temperature to result in formation of solid constituents. More preferably, the reaction should be carried out by contact- reaction at -70-70 °C, or most preferably at -50-50 °C. After the contact-reaction, the reacting temperature is slowly raised for sufficient reaction for the duration of 0.5 - 5 hours at 50 - 150°C.
- the particles of said solid catalysts obtained during the above process can be further reacted with the titanium compounds.
- These titanium compounds are titanium halides or halogenated alkoxy titaniums respectively with an alkoxy functional group of 1 - 20 carbons. At times, a mixture of these compounds can also be used. Of these compounds, however, a titanium halide or a halogenated alkoxy titanium compound having an alkoxy functional group of 1-8 carbons can be appropriately used, or more preferably a titanium tetrahalide can be used.
- the catalyst produced according to the process of the present invention can be utilized for homo- or co-polymerization of ethylene.
- the catalyst is used in homo- polymerization of ethylene, and also in co-polymerization of ethylene and -olefin such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, or 1-hexene having three or more carbons.
- the polymerization reaction in the presence of a catalyst in the present invention is carried out by means of using (i) a solid complex titanium catalyst of the present invention, comprising magnesium, titanium, halogen, and an electron donor, and (ii) a catalyst system comprising compounds of organic metals of Groups II or HI of the Periodic Table.
- the solid complex titanium catalyst constituent can be used as a component in the polymerization reaction after pre-polymerization with ethylene or -olefin.
- the pre-polymerization can be carried out in the presence of a hydrocarbon solvent such as hexane, at a sufficiently low temperature, with ethylene or ⁇ -olefin under pressure, in the presence of the above catalyst constituent and such organic aluminium compound as triethyl--luminium.
- the pre-polymerization by maint--uning the shapes of catalysts by surrounding the catalyst particles with polymers, is helpful in producing good-quality post- polymerization shapes of polymers.
- the weight ratio of polymers to catalysts after pre- polymerization is ordinarily 0.1:1 - 20:1.
- the organometallic compound in the present invention can be represented by a general formula of MR n , wherein, M stands for a metal constituent of Group H or IDA. in the Periodic Table, such as magnesium, calcium, zinc, boron, aluminium, and gallium, R for an alkyl group with 1 - 20 carbons, such as a methyl, ethyl, butyl, hexyl, octyl, or decyl group, and n for the atomic valence of the metal constituent.
- M stands for a metal constituent of Group H or IDA. in the Periodic Table, such as magnesium, calcium, zinc, boron, aluminium, and gallium
- R for an alkyl group with 1 - 20 carbons, such as a methyl, ethyl, butyl, hexyl, octyl, or decyl group
- n for the atomic valence of the metal constituent.
- a trialkyl aluminium having an alkyl group of 1 - 6 carbons such as triethyl-durmnium and t-riisobutylaluminium, or the mixture thereof can be utilized.
- an organic aluminium compound having one or more halogen or hydride groups such as ethyl--iuminium dichloride, diethyl-duminium chloride, ethylaluminium -ye-sgr ⁇ chloride, or ⁇ -iisobuty uminium hydride can also be used.
- the polymerization reaction it is possible to carry out either the gas phase or bulk polymerization in the absence of an organic solvent, or the liquid slurry polymerization in the presence of an organic solvent. These polymerization methods, however, are carried out in the absence of oxygen, water, or other compounds that may act as catalytic poison.
- the concentration of the solid complex titanium catalyst (i) with respect to the polymerization reaction system, in case of liquid phase slurry polymerization, is approximately 0.001 ⁇ 5 mmol in terms of titanium atoms in catalyst per one liter of the solvent, or more preferably approximately 0.001 ⁇ 0.5 mmol.
- alkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane
- alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene
- halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene; and the mixtures thereof.
- the amount of the solid complex titanium catalyst (i) should be approximately 0.001 - 5 mmol in terms of titanium atoms in catalyst per one liter of the polymerization reactant, preferably approximately 0.001 - 1.0 mmol, or more preferably approximately 0.01 - 0.5 mmol.
- the preferable concentration of the organometallic compound (ii), as calculated by organometallic atom, is about 1 - 2,000 mol per mole of titanium atoms in catalyst (i), or more preferably about 5 - 500 mol.
- the polymerization herein is carried out at a sufficiently high temperature, regardless of the polymerization process.
- the temperature of approximately 20 - 200 °C is appropriate, or more preferably approximately 20 - 95 °C.
- the appropriate pressure of monomers at the time of polymerization is the atmospheric to 100 atm, or more preferably 2 - 50 atm.
- melt index ASTM D 1238
- the value of the melt index generally becomes greater as the molecular weight decreases.
- the products obtained by the method of polymerization of the present invention are solid ethylene homo-polymers or the copolymers of ethylene and ⁇ -olefin, which have excellent bulk density and fluidity. Since the yields of polymer are sufficiently high, there is no need for the removal of catalyst residues.
- a solid complex titanium catalyst was produced by means of the following three steps: (i) Step : Production of magnesium solution
- the temperature of the reactor was lowered to room temperature, and an excessive amount of ethanol solution was added to the polymerized matters.
- the polymer thus produced was collected by separation and was dried in an oven at 50 °C for at least six hours, whereby polyethylene was obtained in the form of white powder.
- the polymerization activity (kg of polyethylene divided by gram of catalyst) was calculated as the weight (kg) ratio of the polymers as produced per the amount of catalysts so used (gram of catalyst).
- the results of polymerization are shown in Table 1, together with the bulk density (g ml) of the polymers, and the melt index (g 10 minutes).
- EXAMPLE 2 As in Step (i) of Example 1, 100ml of decane was used while producing magnesium solution under the same conditions. Then, 200ml of mineral oil was added thereto for adjusting the viscosity therein to produce catalysts as in Example 1. The titanium content of the catalyst thus produced was 5.2wt%. The polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
- Step (i) of Example 1 150ml of decane was used while producing magnesium solution under the same conditions. Then, 150ml of mineral oil was added thereto for adjusting the viscosity therein to produce catalysts as in Example 1. The titanium content of the catalyst thus produced was 4.8wt . The polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
- Step (i) of Example 1 200ml of decane with 100ml of mineral oil were used while producing magnesium solution under the same conditions, and thus the catalysts were produced as in Example 1.
- the titanium content of the catalyst thus produced was 5.1wt%.
- the polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2000-0066411A KR100389475B1 (en) | 2000-11-09 | 2000-11-09 | Preparation method of catalyst for ethylene polymeration or copolymeration |
KR2000066411 | 2000-11-09 | ||
PCT/KR2001/001904 WO2002038619A1 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo- or co- polymerization of ethylene |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1355952A1 true EP1355952A1 (en) | 2003-10-29 |
EP1355952A4 EP1355952A4 (en) | 2005-01-12 |
EP1355952B1 EP1355952B1 (en) | 2006-08-23 |
Family
ID=19698065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01983847A Expired - Lifetime EP1355952B1 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo- or co- polymerization of ethylene |
Country Status (9)
Country | Link |
---|---|
US (2) | US6897274B2 (en) |
EP (1) | EP1355952B1 (en) |
JP (1) | JP3950051B2 (en) |
KR (1) | KR100389475B1 (en) |
CN (1) | CN1213075C (en) |
AT (1) | ATE337342T1 (en) |
AU (2) | AU2002212771A1 (en) |
DE (1) | DE60122581T2 (en) |
WO (1) | WO2002038619A1 (en) |
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KR100546499B1 (en) * | 1999-05-27 | 2006-01-26 | 삼성토탈 주식회사 | A catalyst for ethylene homo- and co-polymerization |
KR100389475B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
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WO2003099749A1 (en) * | 2002-05-24 | 2003-12-04 | Idemitsu Kosan Co., Ltd | Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization and method for producing polyolefin |
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CN105440174B (en) * | 2014-08-15 | 2017-12-19 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and application |
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DE102017210582A1 (en) | 2017-06-23 | 2018-12-27 | Bayerische Motoren Werke Aktiengesellschaft | Internal combustion engine |
WO2018233974A1 (en) | 2017-06-23 | 2018-12-27 | Bayerische Motoren Werke Aktiengesellschaft | Internal combustion engine |
DE102018207829A1 (en) | 2018-05-18 | 2019-12-05 | Bayerische Motoren Werke Aktiengesellschaft | Internal combustion engine |
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CN1213075C (en) | 2005-08-03 |
EP1355952A4 (en) | 2005-01-12 |
EP1355952B1 (en) | 2006-08-23 |
KR20020036287A (en) | 2002-05-16 |
US20040063571A1 (en) | 2004-04-01 |
AU2002212771A1 (en) | 2002-05-21 |
JP3950051B2 (en) | 2007-07-25 |
US6916759B2 (en) | 2005-07-12 |
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DE60122581D1 (en) | 2006-10-05 |
US6897274B2 (en) | 2005-05-24 |
CN1503810A (en) | 2004-06-09 |
DE60122581T2 (en) | 2006-12-14 |
AU2002215244A1 (en) | 2002-05-21 |
JP2004513989A (en) | 2004-05-13 |
KR100389475B1 (en) | 2003-06-27 |
WO2002038619A1 (en) | 2002-05-16 |
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